Water-repellent textile material and method of producing the same



Patented May 5, 1925.

1,53 ,254 UNITED ,s A ss PATENT OFFICE.

CLARENCE B. WHITE, 01 HONTCLAIR, NEW JERSEY, ASSIGNOR TO FRED S. BENNETT, 1110., OF NEW YORK, N. Y., A. CORPORATION OF NEW YORK.

-WA'1ER-REPELLENT TEXTILE MATERIAL AND METHOD OF PRODUCING THE SAME.

No Drawing.

To a ll 'whom it may concern: I

Be it known that I, CLARENCE B. WHITE,

a citizen of the United States of America, residing at Montclair, in the county .of Essex and State of New Jersey, have invented certain new and useful Improvements in ater-Repellent Textile 7 Material and Methods of Producing the Same, of which the following is afull, clear, and exact de; scription. a,

This invention relates to waterproofed and preserved textile materials and to -methods of preparing the same, more par-' ticularly materials in which the fibres thereof are impregnated, coated, or otherwise treated with compounds of rare earth metals such as thorium, cerium, lanthanum, didymium (neodymium and prazeodymium),

' zirconium and uranium. The chief object of the invention is to provide textile materials which are not only highly repellent to water but which are not materially impaired in that quality by treatment with gasoline, benzene, naphtha, and other hydrocarbons such, for example, as are employed in so-called dry-cleaning, In carrying out the invention in the preferred manner the substances used for giving the fabric or other fibrous material the desirable prop erties of water-repellency, resistance to inurious influences of atmospheric gases, etc are what may for convenience be termed metallic soaps of the rare earths, that is, fatty-acid salts of such elements; and espec1al1y salts of the higher organic acids and their derivatives, for example acids of the eneral' type C H O the oleic series, type H,,,2O,; the linoleic series, type 0,31 10 the linolenic series, type 0,11 ,60 the chaulmoogric cyclic series, type Of the com ounds or rare earth elements and acids 0 the kind indicated, such metallic soaps as oleates, linoleates, alphaelaeostearates, and abietates are in general, when freshly precipitated, fairly soluble. in heated ether, turpentine, gasoline, etc., while metallic soaps of. the higher acids, for example stearates, elaidates,l betaelaeostearates, and palmitates are only very sparingly soluble in ether,'hot or cold, and still less so in turpentine, gasoline, benzene, and

other, 1i uid hydrocarbons. Such salts are j alsohi yresistant to alkali, whether caustic or car onate, and'when decom osed thereby, at all, they-are converte into insol Application 'filed December 9, 1922. Serial 1W0. 605,984. I

uble hydroxidsor carbonates. For example, the fatty acid soap cerium palmitate is almost completely insoluble in tur ntine and benzol, and in hot ether is solub e only to the extent of about 0.8 per cent.

Heretofore, aluminum hydroxid or aluminum soap has been used to give waterrepellency to textile materials, but each of ,these compounds is readily converted, on

are not soluble in the re-agent and hence remain in the fabric, which therefore iretains its water-repellent quality.

This characteristic of the salts of rare earth elements, namely, their relative inertness. to alkalis,-renders them es ecially advantageous for the treatment 0 textile materials to make the same water-repellent,

or to serve as mordants for dyes or form insoluble lakes on the fibre. Moreover, they are antiseptic'in character, and hence resist mildew and spore growth, which further distinguishes them from aluminum salts in general use for treating fabrics,

As explained in my copendm application Serial No. 639,219, when a abric has been treated with a soluble metallic salt which is absorbed by the fibres thereof, and the salt has been converted by chemical or electrolytic action into an insoluble compound, as for example into a hydroxid,

phosphate, fluorid, .chromate, tungstate,

stannate, etc., the fabric becomes repellent to water. This re llency appears to be internalfl that is, ue to "an actual absorption by the-fibres, rather than surface repelleney producedby coating the fibres. 'I

ave discovered that if a fabric so treated be a ain treated with a metallic salt, referab y a rare earth salt, and this sh t be converted into an insoluble compound, the fabric has imparted to it. a high degree of surface repellency and also has its Inits water-repellency.

ternal repellenc increased. Moreover, the capillarity of t e fabric is almost if not wholly destroyed. In one of these treatments an aluminum salt may be used, with or without a rare earth salt in the same treatment, for the reason that the presence'of the rare earth in'one or both coatings or impregnations renders the aluminum salt much more stable and difiicult of removal from the fibre by caustic alkali.

In carrying out my invention, advantage may be taken of the fact, stated above, that freshly precipitated oleate, linoleate, abietate, etc., are soluble in hydrocarbon solvents, especially when the solvent is hot. Hence the desired treatment can be affected by passing the fabric or fibres (or, in general, the textile material) through a Warm or hot solution of the selected metallic chlorid of cerium, thorium, or lanthanum,

etc., or acetate, formate, sulfate, sub-nitrate, or chlorid of one or more of such metals. As a result, an insoluble fatty acid compound of the metal or metals is formed or precipitated in the textile'material, rendering the latter highly repellent to water, noncapillary, and capable of being washed with soap and of being cleaned with gasoline and other hydrocarbon agents without loss of Of course, in this double treatment, fatty acid soaps of the rare earth metals which are soluble in hydrocarbon solvents, as for example oleates, linoleates, etc., may be used if desired.

In some cases the soluble metallic soap or soaps used may be replaced by an emulsion of a fatty acid compound, as for example an emulsion of Japan wax. To such emulsions rubber, parai'fin, ceresin, or other Wax capable of being emulsified, can be added, which will be deposited on the fibres or within the pores thereof without thereby interfering with the reaction between the metallic soap and the solution with which the fabric. is afterwards treated.

It is not essential, in all cases, that the textile material be treated first with the soap compound, inasmuch as excellent results can be obtained by reversing the order; impregnating in the first instance with the soluble salt and then passing the material through the soap solution. In this order of treatment, however, the acid salts employed (say the chlorid, acetate, sulfate, etc.) have a tendency to precipitate the soap or break the emulsion and as a result the fabric or fibres are apt to be marred by deposition of flakes of soap or by solid particles of the emulsion, especially where waxes or rubber compounds are used in the emulsion.

An alternative mode of depositing a metallic soap upon or within the fibres is to first deposit the metallic element in the form of an insolublecompound which is decomposable by a fatty acid, as for example a carbonate or hydroxid of the selected metal or metals, and then treat the material with a fatty acid, or acids, such as oleic, stearic, palmitic, etc., with resulting conversion of the carbonate or hydroXid into the corresponding fatty acid salt or metallic soap. In this procedure the deposition of the insoluble compound can be efiected by the method described in my copending application above mentioned.

In general, metallic soaps can be deposited: (1) By direct deposition from a solution; (2) By the action of a fatty acid, such as stearic, oleic, palmitic, etc., upon rare earth carbonate or hydoxid freshly precipitated on or in the fibres; and (3) By the interaction of soluble rare earth salt (say a chlorid, acetate, sulfate, etc.) and an alkali salt of the desired fatty acid, as for example sodium, potassium or ammonium stearate, palmitate, oleate, elaidate, etc. In the second of these methods the resulting salts are almost invariably of an acid type; while in the second, which depends upon double decomposition, normal neutral salts are produced if precautions are taken to avoid excess of the rare earth salt or of the fatty acid salt.

For some purposes it is advantageous to first deposit on the fibres an insoluble rare earth compound, such as a carbonate, hydroxid, phosphate (or tho-, meta-), hypophosphate, etc., preferably carbonate, hydroxid or phosphate. This gives the subsequently deposited metallic soap an underlying basis which is itself repellent and capable of neutralizing or resisting to a considerable extent at least, the action of atmospheric gases, such as carbon dioxid and traces of sulfuric and nitric acids. The fabric is thus able to resist the destructive influences of such atmospheric agencies to a much greater degree than is an untreated fabric. When fabric is painted and thereby impregnated with drying oils, slow hydrolysis takes place, especially when exposed to light, and the drying oils set free organic acids which attack the fibre. If there is an underlying metallic hydroxid or carbonate (for example) the fatty acid combines therewith to form a metallic soap .as it has a marked protective effect against the destructive action of air, light and moisture. The desired insoluble rare earth compound can be deposited on the fibres by first treating with a soluble rare earth salt, say a chlorid, acetate, or nitrate, drying the material; and then treating with an alkaline carbonate, hydrate, sulfid, or the like. At-

' ter this treatment (in which double decomposition takes place) the material can be tit freed from alkalin salts by washing with water. In somecases a rare earth phosphate is advantageous as the underlying coating; such phosphates being in general very insoluble and tending to make dyes faster, especially direct dyes.

Variousways of carrying out my invention in practicewill now be given; it being understood, however, that the invention is not limited to the specific details or materials set forth. In general the fabrics (or fibres, as the case may be) need not be subjeoted to treatment. longer than is necessary for thorough wetting, after which they are dried, being first s uee zed to eliminate as much as possible 0 the treating liquid or emulsion, in order to'avoid loss, as by evaporation. v 1,

(A) For direct deposition of metallic soap: A ten per cent solution oi? cerium, thorium, lanthanum or didymium oleate or linoleate, in varnoline or gasoline. Use ttm r a fin b or 1m regna ion an proo y double decompiisition: (1) Stearate 0% sodium, five per cent aqueous solution. Use

hot. Impregnate the. textile material, dry the same, and pass through five per cent aqueous solution of, cerium or thorium acetate. (2) Five per cent aqueous solution of a mixture composed of cerium acetate two parts (by weight), lanthanum acetate one part, didymium acetate one part. Dry, and pass through five per cent solution of sodium, potassium or ammonium stearate or p'almitate.

(C) With an emulsion of Japan wax (largely stearicand palmi-tie acids): llen per cent emulsion in water at about 140 F. impregnate, squeeze, and pass through fiye per cent aqueous cold solution of thorlum acetate-nitrate; or through hot or cold five per cent solution of acetate (or chlorid, sulfate, etc.) of cerium two parts, of lanthanum one part, and of didymium one part. v

(1D) Stearic acid twenty-six parts, oleic acid 12 parts, parafiin thirty-six parts,

saponified with caustic soda twenty-six parts; in eight hundred parts water. Im-

pregnate, and pass through either of the to render the same water-repellent, comprisa solution of alkalin hydrate (sodium, po-

tassium or ammonium hydrate), rinse and dry; pass through five per cent solution of sodium stearate, then through five per cent solution of cerium (or lanthanum or didymium) acetate, wash, and dry. Or: Pass the material through a five to ten per cent solution of a soluble thorium salt or its.

equivalent in cerium, lanthanum and (or) didymium. Dry, and pass through alkalin through a J apanwax emulsion (saponified) of a strength indicated by five to ten parts in ninety-five to ninety parts water, at 140 to 150 F. Then passthrough a five pc 7 cent rare earth salt in water.

The invention is applicable to a large variety of textile materials (using the latter to include woven, felted, knit, netted, and other fabrics, threads, yarns, warps, fibres, etc.) of vegetable or animal origin, as for example cotton, silk and wool.

It is to be understood that the invention is not limited to the details herein described but can be carried out in other ways without departure from its spirit as defined by the appended claims.

I claim- 1. Water-repellent textile material impregnated with a fatty acid compound of a rare earth metal.

2. Water-repellent textile material impregnated with a metallic soap which is,

at most, sparingly soluble in hydrocarbons.

3. Water-repellent textile material impregnated with a rare earth compound of a fatty acid of the type C H O 4. Water-repellent textile material impregnated with an insoluble inorganic rare earth metal compound and with an insoluble organic rare earth metal compound.

5. A process of rendering textile material water-repellent, comprising impregnating the material with a fatty acid compound of a rare earth metal.

6. A process of treating textile material ing treating the material with a solution hydrate or sulfid solution, wash and dry.

of a fatty acid compound of an alkali metal, and with a solution of a salt of a rare earth metal.

7. A process of treating textile material to render the same water-repellent, comprising depositing on the fibres of the material.

an insoluble inorganic compound of a rare earth metal, and impregnating the material with a fatty acid compound of a rare earth 10 metal.

8. A process of treating textile material to ateaane render the same water-repellent, comprising depositing on the fibres of the material an insoluble inorganic compound of a rare earth metal, and treatin the material with a solution of a fatty acld compound of an alkali metal, and with a solution of an inorganic salt of a rare earth metal.

In testimony whereof 1 hereto 'atfix my signature.

CLARENCE B. WHITE. 

